JP6498945B2 - Power storage device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a power storage device capable of storing lightning and atmospheric current and a method for manufacturing the same.

  Capacitors are electronic parts that store or discharge electric charges (electric energy) by electrostatic capacity. Power supply stability, backup circuits, coupling elements, noise filters, etc. in mobile electronic devices such as personal computers and mobile phones. It is an indispensable part for electronic equipment. In recent years, high-function IT products such as mobile phones and ultra-small storage devices and batteries for electric vehicles have rapidly evolved, and the demand for capacitors that are even smaller, have a large capacity, and have high functions such as memory is increasing. In particular, products that meet green innovation (low carbonization) are required to prevent global warming.

  The classification according to the use of the capacitor is roughly divided into a high voltage power circuit and an electronic circuit. Among these, as a large-capacity capacitor for a high-voltage power circuit, an electric double layer capacitor has attracted attention and has recently been expected to be used for electric storage. Specifically, there are power sources for hybrid vehicles and electric vehicles, power supplies for rapid startup of copy machines, uninterruptible power supplies, train power supplies for railways, etc., with a track record of securing a starting power of about 2%.

A power storage unit using a capacitor is widely used as a main component of electronic / electric equipment from 1 pF to several tens of mF. The storage capacity C (F) is C = Q / V = εA / d (Q (Q): electric charge, V (V): voltage, ε: dielectric constant, A (m ² ): electrode area, d (m): Therefore, the higher the electrode area and the smaller the electrode distance, the higher the charge capacity. However, from the viewpoint of light and thin electronic / electric equipment and the required storage capacity, the electrode area A is increased to reduce the inter-electrode distance d to the maximum capacity, or the electrode area A is decreased to reduce the distance between the electrodes. It is currently difficult to increase the distance d to a minimum capacity.

Regarding the electric storage body, the present inventor considered that the electric charge is direct current or alternating current in a Si— (Al, Ti, V) alloy obtained by surface extraction removal of Al, Ti, V, and a TiO ₂ coated Ti—Ni—Si based amorphous alloy. It was discovered that it can be accumulated regardless. The Si— (Al, Ti, V) alloy is shown in Non-Patent Documents 1, 2, and 3, and the TiO ₂ coated Ti—Ni—Si-based amorphous alloy is shown in Non-Patent Documents 4 and 5.

In addition, research on nanosheet thin film capacitor elements of perovskite Sr ₂ Nb ₃ O ₁₀ and Ca ₂ Nb ₃ O ₁₀ having a dielectric constant of 210 to 240 with a film thickness of 10 nm or less has been reported by the National Institute for Materials Science (NIMS). (Non-Patent Document 6) has a large inter-electrode distance and is not easy to join with an electrode material due to ceramics and has high contact resistance. In addition, a high specific capacity of 1,160 F / cm ³ has been reported in a MnO ₂ -coated nanoporous Au-based amorphous alloy separator in a chemical electrolyte (Non-Patent Document 7), which is also a conventional electrochemical cell. Application.

  More recently, a physical secondary battery having a voltage of 1.5 V, a power of 500 Wh / L, an output density of 8 kW / L, a cycle life of 100,000 times, and an operating temperature range of −25 ° C. to + 85 ° C. has been developed by a Japanese manufacturer (non- In Patent Document 8), an electron trap level is formed in a semiconductor band gap, and charging / discharging is performed depending on whether the level is charged with electric potential or empty, and the voltage is 1.5V. Limited.

M. Fukuhara, T. Araki, K. Nagayama and H. Sakuraba, “Electric storage in de-alloyed Si-Al alloy ribbons,” EuroPhys. Lett., 99 (2012), 47001. M. Fukuhara, “Electric Charging / Discharging Characteristics of Capacitor, Using De-alloyed Si-20Al Alloy Ribbons,” Elect. Electr. Eng., 3 (2), (2013), 72-76. M. Fukuhara and H. Yoshida, “AC charging / discharging of de-alloyed Si-Al-V alloy ribbons,” J. Alloys and Comp., 586 (2014) S130-S133. M. Fukuhara, H. Yoshida, M. Sato, K. Sugawara, T. Takeuchi, I. Seki, and T. Sueyoshi, “Superior electric storage in de-alloyed and anodic oxidized Ti-Ni-Si glassy alloy ribbons,” Phys. Stat. Sol. RRL, 7 (7), (2013), 477-480. M. Fukuhara and K. Sugawara, “Electric charging / discharging characteristics of super capacitor, using de-alloying and anodic oxidized Ti-Ni-Si amorphous alloy ribbons,” Nanoscale. Res. Lett., 9, (2014), 253. M.Osada, K.Akatsuka, Y.Ebina, H.Funakubo, K.Ono, K.Takada and T.Sasaki, Robust high-k response in molecularly thin perovskite nanosheets, ACS NANO, 4,5225-5232 (2010) . X.Y.Lang, A.Hirata, T.Fujita and M.W.Chen, Nature Nanotech., On line (Feb. 20, 2011). Nihon Micronics Co., Ltd., secondary battery battenice, http://www.mjc.co.jp/product/index3.html

  By the way, the earth forms an “earth capacitor” by cosmic rays with the upper layer plus 50 km above the ground and the earth minus, and stores inexhaustible electrical energy permanently. The atmospheric voltage rises with a gradient of 100 V / m. Intrusion of low pressure and volcanic lightning at the time of volcanic eruption are sure examples of evidence that can be observed visually by dielectric breakdown. The lightning discharge voltage is 2 MV to 200 MV, the current is 1 kA to 200 kA, the lightning strike time is 1 ms to 0.5 s, the lightning strike power is about 900 GW on average, and the total integrated power is 250 kWh. The use of the inexhaustible electrical energy of this earth capacitor has been thought by many since the 20th century.

Further, it is reported that atmospheric currents of 300 C / km ² years or less exist even in rainy weather and clear weather other than lightning, and the atmospheric current is 5 to 60 times larger than the lightning current (Chalmers, 1967). Atmospheric current can also be collected even on a clear day, so it can be expected as an electrical energy source for individuals and homes.

  By the way, the number of lightning detections in Japan from 2002 to 2008 is 200,000 to 1,000,000 times / year (Central Research Institute of Electric Power), and the amount of lightning strikes per time is 10 kWh to 500 kWh. 500 GWh can be estimated. On the other hand, since the atmospheric current is 5 to 60 times the lightning current, it can be calculated as 10 GW to 30 TWh. Since Japan's total power generation is about 1,030 TWh / year, it is 0.001% to 3%.

  In order to store the lightning current, it is necessary to satisfy the three conditions of high voltage, high current, withstand voltage that can withstand a short time, withstand current, and short time storage. Moreover, in order to store atmospheric current, although the barrier is lower than the lightning current, it is necessary to satisfy the same three conditions as those of the lightning current.

  However, conventional power storage units use chemical ion transfer, have low response, have a withstand voltage of about 4 V, and so far no power storage units that sufficiently satisfy the above three conditions have existed. Thus, it has been difficult to efficiently store lightning and atmospheric current with the conventional power storage unit.

  In view of the above problems, an object of the present invention is to further develop the above-described research by the present inventor and to provide a power storage device that can efficiently store lightning and atmospheric current, which are natural energy, and a method for manufacturing the same.

According to one aspect of the present invention, comprising: a lightning rod capable of inducing lightning and atmospheric current; and a solid-state electronic storage body having a physical storage capacity for storing lightning and atmospheric current through the lightning rod , The solid-state electronic storage body is composed of a plurality of electric distribution constant type capacitors that shunt lightning and atmospheric current, and each electric distribution constant type capacitor sandwiches the insulating layer with a recess formed on the surface thereof. and a pair of electrodes, said recess, said evenly distributed on the surface of the insulating layer, the density of the recess, the area 1 cm ² per surface of the insulating layer, and wherein der Rukoto 10 ¹⁰ or more A power storage device is provided. The solid-state electronic storage battery has a huge storage capacity of 1 kF / cm ³ or more, and stores lightning and atmospheric current instantaneously for 0.5 s or less. The solid-state electronic storage body is composed of 1,000 or more electric distribution constant type capacitors that shunt lightning and atmospheric current.

Also, in one aspect of the present invention, the recess, and a depth of about less opening diameter 20 nm and 0.5Nm～3nm, the insulating layer that have a less electric resistance 100Tiomega. The insulating layer covers a crystalline or amorphous layer of a metal or alloy of 100 MPa or more. The surface of the insulating layer on which the recesses are formed is an integrated nanostructure, which forms a parallel integrated body of nanocapacitors. The insulating layer is composed of an amorphous phase having an oxygen defect or an organic polymer. The insulating layer has a withstand voltage of 1 kV or more. The solid state electronic storage body can operate at −269 ° C. to 600 ° C. The solid electronic power storage unit may be configured in a square shape, a folded shape, a tape measure shape, or a spiral shape.

  In one embodiment of the present invention, the material of at least the tip of the lightning rod is made of chromium-coated brass, aluminum, or stainless steel. It further includes a plurality of backflow prevention diodes connected between the lightning rod and each of the electric distributed constant capacitors, each having a threshold voltage of 0.4 V or less.

According to another aspect of the present invention, there is provided an insulating layer in which concave portions are formed so as to be uniformly distributed on the surface, and the density of the concave portions is 10 ¹⁰ or more per 1 cm ² of the surface area of the insulating layer. A step of forming the insulating layer , a step of manufacturing an electric distributed constant capacitor by sandwiching the insulating layer between a pair of electrodes, and a plurality of electric distributed constant type capacitors connected in parallel, whereby lightning and air And a step of producing a solid-state electronic power storage unit having a physical power storage capacity for storing a current.

  In another embodiment of the present invention, the step of forming the insulating layer may form an oxide film having a recess formed on the surface by using an anodic oxidation method in a fluorine-containing solution or in perchloric acid. . Or the process of forming an insulating layer may form the insulating layer which consists of an organic polymerization polymer by which the recessed part was formed in the surface by sputtering.

ADVANTAGE OF THE INVENTION According to this invention, the electrical storage apparatus which can store efficiently the lightning and atmospheric current which are natural energy, and its manufacturing method can be provided. Therefore, it can greatly contribute to energy saving, new energy, and CO ₂ reduction. In addition, power storage using medium-scale lightning has the effect of suppressing the occurrence of large-scale lightning, which can contribute to disaster prevention and environmental protection.

FIG. 1 is a schematic diagram illustrating an example of a power storage device according to an embodiment of the present invention. FIG. 2A is a schematic cross-sectional view showing an example of an electric distributed constant capacitor according to an embodiment of the present invention, and FIG. 2B is a partially enlarged view of FIG. FIG. 3 is a scanning electron micrograph of the surface of the insulating layer in which concave portions with an average of 3 nm are formed. FIG. 4 is a circuit diagram of an electric distributed constant capacitor according to an embodiment of the present invention. Fig.5 (a)-FIG.5 (c) are schematic which shows an example of the shape of the solid-state electrical storage body which concerns on embodiment of this invention. FIG. 6A to FIG. 6C are process cross-sectional views illustrating an example of a method for manufacturing a power storage device according to an embodiment of the present invention. FIG. 7 is a graph showing the relationship between the average concave dimension and the electric capacity in the series circuit.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the description of the drawings, the same portions are denoted by the same reference numerals, and description thereof is omitted.

<Configuration of power storage device>
As shown in FIG. 1, a power storage device according to an embodiment of the present invention includes a lightning rod 1 capable of inducing lightning and atmospheric current, and a physical power storage capacity for storing lightning and atmospheric current through the lightning rod 1. A solid-state electronic storage battery 2 having Here, the “physical power storage capability” means the performance of storing power using the movement and storage of physical electrons themselves, not electrochemical ion migration.

  The shape of the lightning rod 1 is not specifically limited, For example, the shape similar to the conventional lightning rod can be employ | adopted. It is preferable to use a material having a large lightning effect such as chromium-coated brass, aluminum (Al), and stainless steel for at least the tip portion of the lightning rod 1. By using these substances, lightning and atmospheric current can be efficiently dielectrically generated even in rainy weather other than lightning and in fine weather.

  The material of the lightning rod 1 can be appropriately selected according to the polarity of lightning and atmospheric current. Since chrome-coated brass and Al are negatively charged, they are suitable for large-scale positive voltage drop and winter electricity storage. On the other hand, since stainless steel is positively charged, it is suitable for summertime negative voltage drop and atmospheric current storage. Therefore, a lightning rod 1 made of chromium-coated brass or Al is used for large positive lightning strikes or lightning strikes in winter, and a lightning striker 1 made of stainless steel is used for negative polarity lightning or atmospheric current storage in summer. By selectively using it, it is possible to effectively store lightning currents and atmospheric currents having different polarities.

  The lightning rod 1 is installed at any place on the earth. In addition, since the atmospheric voltage rises with a gradient of 100 V / m, power storage in high mountains is effective other than lightning power storage. Especially in mountainous areas and the sea where water vapor and clouds are easily applied, the humidity becomes 50% or more, which is an extremely favorable condition for power storage.

The solid-state electronic storage body 2 has a huge storage capacity of, for example, 1 kF / cm ^{3 to} 10 kF / cm ³ and has a current resistance characteristic that can withstand high currents of lightning and atmospheric current. Note that the power storage capacity of the solid-state electronic power storage unit 2 may be 10 kF / cm ³ or more. The solid-state electronic storage body 2 stores lightning and atmospheric current instantaneously for about 1 ms to 0.5 s, more preferably 1 ms or less.

The solid-state electronic storage battery 2 includes a plurality of (n) shunt solid-state electronic storage batteries (EDCC, Electric Distributed Constant Capacitor) 2 ₁ , 2 ₂ , which store light by dividing lightning and atmospheric current. 2 ₃ ... 2 _n . The number n of the electric distribution constant type capacitors 2 ₁ to 2 _n is, for example, 1,000 to 100,000, and can be appropriately selected according to desired current resistance characteristics. Each of the electric distributed constant type capacitors 2 ₁ to 2 _n is connected in parallel to the lightning rod 1 via backflow prevention diodes (VF effect diodes) D ₁ , D ₂ , D ₃ ,..., D _n . .

The backflow prevention diodes D _{1 to} D _n prevent back flow of lightning and atmospheric current stored in the respective electric distribution constant type capacitors 2 ₁ to 2 _n . Specifically, lightning strikes consist of a precursor discharge in which a streamer extends from the cloud toward the ground, and a return electric shock that rises from the ground toward the cloud as soon as it approaches the ground. By attaching the backflow prevention diodes D _{1 to} D _n to the lightning rod 1, it is possible to prevent discharge from the power storage unit due to return electric shock. Since it is better for the forward voltage (threshold voltage) Vf to be small during power storage, the threshold voltage Vf of the backflow prevention diodes D _{1 to} D _n is preferably 0.4 V or less, and more preferably 1 V or less.

Each of the electric distributed constant capacitors 2 _{1 to} 2 _n includes a base 10, insulating layers 11 and 12 covering both surfaces of the base 10, and the base 10 and the insulating layers as schematically shown in FIG. A pair of electrodes 13 and 14 sandwiching 11 and 12 is provided. In FIG. 2 (a), the insulating layers 11 and 12 cover both surfaces of the substrate 10. However, either one of the insulating layers 11 and 12 is not present and only one surface of the substrate 10 is covered. May be. In that case, the base 10 and the electrodes 13 and 14 on the side where the insulating layers 11 and 12 are not provided are directly joined.

  As the substrate 10, a metal or alloy crystal, amorphous, or resin can be used, and a tough material of 100 MPa or more is preferable. Examples of the metal or alloy material include zinc (Zn), aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf), tin (Sn), niobium (Nb), tantalum (Ta), and tungsten. (W) and molybdenum (Mo). Among these materials, it is possible to form a firm and high resistance oxide film after oxidation by anodizing, and to form a sub-nanometer or nanometer-size recess as described later on the surface of the oxide film, and at a low cost. For this reason, simple metals or alloys of Al, Ti, and Nb are preferable.

  The thickness of the insulating layers 11 and 12 is about 200 nm to 20 μm. The insulating layers 11 and 12 have an electrical resistance of about 0.1 kΩ to 100 TΩ, and preferably about 1 kΩ to 100 TΩ. The electrical resistance is less likely to be stored as the resistance is smaller than 0.1 kΩ, and the discharge performance is degraded as the electrical resistance is larger than 100 TΩ. .

  The withstand voltage of the insulating layers 11 and 12 is, for example, 1 kV or more, more preferably 10 kV or more, and more preferably 100 kV or more in order to withstand high voltages of lightning and atmospheric current. However, it is better not to let large thunders with a small number of 100 kV or more escape to the ground and store them. Power storage from medium-scale lightning also has the effect of suppressing the occurrence of large-scale lightning, so power storage targets medium- and small-scale lightning and atmospheric current storage.

As a material of the insulating layers 11 and 12, an amorphous phase oxide having oxygen defects, an organic polymer, or the like can be used. Examples of the oxide having an oxygen defect include alumina (Al ₂ O ₃ ) and titania (TiO ₂ ). The insulating layers 11 and 12 may be of the same type, or may be of different types, such as one being an oxide and the other being an organic polymer.

As schematically shown in FIGS. 2 (a) and 2 (b), the surface of the insulating layers 11, 12 facing the electrodes 13, 14 has a large number of sub-nanometers or nanometer-sized openings. The recesses 11a and 12a are formed in a self-organizing manner. The recesses 11a and 12a are preferably distributed uniformly on the surfaces of the insulating layers 11 and 12. The density of the recesses 11a and 12a is preferably 10 ¹⁰ or more, more preferably 10 ¹⁴ or more per 1 cm ^{2 of the} surface area of the insulating layers 11 and 12. FIG. 3 shows a photograph of the surface of an insulating layer (titanium oxide film) of sample number 2 in an example described later, observed with a scanning microscope (SEM).

  Each recessed part 11a, 12a functions as a minute capacitor (nanocapacitor) that accumulates electric charges in an electric double layer between the electrodes 13, 14 by having an opening diameter of sub-nanometer or nanometer dimension. For this reason, the entire surfaces of the insulating layers 11 and 12 have integrated nanostructures (cells) to form a parallel assembly of nanocapacitors. In the embodiment of the present invention, the “integrated nanostructure” is a regular assembly of one-dimensional dots, wires, two-dimensional planes, and three-dimensional solids having a nanometer size structure having various functions by various methods. Means an organization.

As shown in FIG. 4, each of the electric distributed constant capacitors 2 _{1 to} 2 _n becomes a distributed constant circuit having nanocapacitors C connected in parallel over the entire surfaces of the insulating layers 11 and 12, and the amount of stored charge per unit area Can be made as large as possible. Since the number of parallel junctions of the nanocapacitor C is proportional to the area of the insulating layers 11 and 12 and the electrodes 13 and 14, the amount of stored charge can be adjusted from the minimum to the maximum.

  As shown in FIG. 2B, the opening diameter d1 and depth d2 of the recesses 11a and 12a can be appropriately selected by adjusting the type and composition of the constituent elements of the insulating layers 11 and 12, the formation method, and the like. It is. The opening diameter d1 of the recesses 11a and 12a is preferably about 50 nm or less, and more preferably about 20 nm or less. The opening diameter d1 of the recesses 11a and 12a is, for example, about 0.5 nm to 50 nm. The smaller the opening diameter d1 of the recesses 11a, 12a, the higher the electric capacity of the nanocapacitor constituted by the recesses 11a, 12a. From the viewpoint of increasing the electric capacity, the opening diameter d1 of the recesses 11a, 12a. Is preferably as small as possible. The value of the opening diameter d1 of the recesses 11a and 12a is the average pore diameter of several to several tens of micropores observed using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). It is calculated as the average value of.

  The depth d2 of the recesses 11a and 12a is, for example, preferably about 0.5 nm to 5 nm, more preferably about 0.5 nm to 3 nm, from the viewpoint of avoiding repulsion between electrons in the aspect ratio d2 / d1. Note that when the recesses 11a and 12a penetrate the insulating layers 11 and 12 like nanotubes, charge leakage occurs and the storage effect disappears. Therefore, the depth d2 is set so that the recesses 11a and 12a do not penetrate the insulating layers 11 and 12. Adjusted.

  Since the electrodes 13 and 14 need to be bonded to the convex oxides of the concave portions 11 and 12, titanium (Ti), chromium (Cr), copper (Cu), nickel (Ni), gold (Au), stainless steel In addition, a conductive material such as molybdenum (Mo) can be used, and the same material may be used, or different materials may be used. For example, the electrode 13 is a positive electrode and the electrode 14 is a negative electrode.

Various shapes can be adopted as the shape of the solid-state electronic storage battery 2 and can be appropriately selected according to the application. For example, it may be a square in which the electric distribution constant type capacitors 2 ₁ to 2 _n are two-dimensionally spread. Further, as schematically shown by solid lines in FIG. 5A to FIG. 5C, a system in which each of the electric distribution constant type capacitors 2 ₁ to 2 _n is stacked (folded shape) and wound up two-dimensionally. A method (winding tape shape) and a three-dimensional spiral winding method (twisting shape) may be used.

  In addition, the power storage device according to the embodiment of the present invention can operate from extremely low temperature (for example, −269 ° C.) to 600 ° C. Therefore, it can be used even in the harsh environment of a desert area or a mountainous area.

As described above, according to the power storage device according to the embodiment of the present invention, a physical giant power storage capability of about 1 kF / cm ^{3 to} 10 kF / cm ³ is achieved by using an extremely small integrated nanostructure. In addition, a next-generation power storage unit that can operate from an extremely low temperature of about −269 ° C. to 600 ° C. can be realized. By constructing the solid-state electronic storage unit 2 by connecting approximately 1,000 to 100,000 units of this storage unit as the electric distributed constant type capacitors 2 ₁ to 2 _n , a high current of lightning or atmospheric current is shunted. It can be stored, and withstand voltage characteristics up to about 10 kV, current resistance of about 100 kA, and instantaneous power storage of about 1 ms or less can be achieved.

  In addition, since the solid-state electronic storage battery 2 is a solid system, there is no possibility of damage due to impact, earthquake, etc. In addition, unlike a conventional secondary battery, the solid-state electronic storage body 2 has a physical storage capacity without an electrochemical reaction. It has advantages such as the fact that there is no limit on the number of discharges, the mountains with severe temperature conditions, the desert environment, the sea surface that requires corrosion resistance, and the use in seawater.

<Method for manufacturing power storage device>
Next, an example of a method for manufacturing the power storage device according to the embodiment of the present invention will be described with reference to FIGS. 6 (a) to 6 (c). In addition, the manufacturing method demonstrated below is an example to the last, and is not limited to this.

  First, as shown in FIG. 6 (a), a substrate 10 made of an amorphous alloy or the like from an alloy ingot arc-melted to a predetermined composition in an argon (Ar) atmosphere by a single roll liquid quenching method under He atmospheric pressure or the like. Is made.

  Next, as schematically shown in FIG. 6B, the base 10 is immersed in an acidic solution by an atomic dissolution removal method (dealing method) to dissolve an electrochemically base metal element (for example, Ni). Thus, atomic holes 11b and 12b having an atomic radius size are formed. This step facilitates anodization described later.

  Next, as shown in FIG. 6C, a large number of sub-nanometer or nanometer-sized recesses 11a and 12a are formed on both surfaces of the substrate 10 by using an anodic oxidation method in a fluorine-containing solution or in perchloric acid. Insulating layers (oxide films) 11 and 12 having a uniform surface are formed. The opening diameters and depths of the recesses 11a and 12a on the surfaces of the insulating layers 11 and 12 can be adjusted by the types of constituent elements, their compositions, processing times, and the like. In addition, when the opening diameters of the recesses 11a and 12a are about 50 nm, the atomic holes 11b and 12b by the dealloying method shown in FIG. 6B are substantially lost, but the opening diameters of the recesses 11a and 12a are small (for example, 5 nm or less). ) In some cases, the atomic holes 11b and 12b are left on the surface by the dealloying method.

  In the case where the organic polymer is coated as the insulating layers 11 and 12, the organic polymer is coated on the surface of the base 10 such as metal or alloy so that the concave portions 11a and 12a are formed on the surface by low-voltage low-temperature sputtering. do it. In this case, the opening diameter and depth of the recesses 11a and 12a can be appropriately adjusted in the sputtering atmosphere, pressure, substrate temperature, time, and the like.

Next, the insulating layers 11 and 12 and the electrodes 13 and 14 are bonded to each other as shown in FIG. 2A by using a micro electro mechanical system (MEMS) method, spot welding, fiber laser, or the like. Thus, each of the electric distribution constant type capacitors 2 ₁ to 2 _n is manufactured. In this way, the required number n of the electric distributed constant type capacitors 2 ₁ to 2 _n are manufactured and connected to the lightning rod 1 through the backflow prevention diodes D _{1 to} D _n , as shown in FIG. The power storage device is completed.

  According to the method for manufacturing a power storage device according to the embodiment of the present invention, a recess having a sub-nanometer or nanometer-size opening diameter is formed on the surface by an anodic oxidation method in a fluorine-containing solution or perchloric acid, or low-voltage low-temperature sputtering. The insulating layers 11 and 12 in which 11a and 12a are uniformly formed can be formed, and the power storage device according to the embodiment of the present invention can be realized.

<Example>
Next, examples of the solid-state electronic storage body 2 of the power storage device according to the embodiment of the present invention will be described. The material to which the present invention is applied is not limited to the materials of the following examples.

Sample Nos. 1, 2, 4 to 6 are sampled from an alloy ingot arc-melted to various compositions in an Ar atmosphere at a cooling rate of 10 ⁶ m / s or less and a single-roll liquid rapid cooling method under He atmospheric pressure (super rapid solidification method). ) And then cut with a cutter to produce a ribbon-shaped sample (substrate) having a width of 1 mm and a thickness of 20 μm. Sample No. 3 was rapidly cooled from an alloy ingot arc-melted to a predetermined composition under an Ar atmosphere by a twin-roll liquid quenching method (super rapid solidification method) at a cooling rate of 10 ⁶ m / s or less and He atmospheric pressure. Thereafter, a ribbon-like sample (substrate) having a width of 1 mm and a thickness of 50 μm was produced.

  As sample numbers 7 to 9, ribbon-like samples (substrates) were prepared by electrolysis using various crystal metals or crystal alloys. As Sample No. 10, an epoxy resin was used to prepare a sample by a mold compression SMC (Sheet Molding Compound) press method. As sample number 11, a ribbon-like sample (substrate) was prepared by a fiber-aggregate multi-layered hand lay-up method using glass fiber reinforced epoxy resin.

Among these, for the ribbon-shaped samples (substrates) of sample numbers 1 to 9, an oxide film covering both surfaces of the substrate was formed using an electrolysis method (anodic oxidation). In the electrolysis method, 1 day HCl treatment at room temperature is performed in advance for 1 day, Ni for sample numbers 1, 2, and 5, Nb for sample number 3, Al, Ni for sample number 4, and sample number For Cu, Fe and Cu were removed, and for Sample No. 7, Al was removed. For sample number 2, the insulating layer 11 is covered with TiO _1.89 and the insulating layer 12 is covered with a polyethylene polymer.

  Further, for the ribbon-shaped sample (substrate) of sample number 10, insulating layers 11 and 12 made of ethylene vinyl acetate copolymer were deposited by using a laser ablation (MAPLE) method. About the ribbon-shaped sample (base | substrate) of the sample number 11, the insulating layer which consists of vulcanized silicon rubber was deposited using the aerosol vapor deposition play deposition (ESDUS, Evaporative Spray Deposition using Ultradilute Solution) method.

Table 1 shows the composition of the matrix (substrate) of the ribbon-shaped samples of sample numbers 1 to 11, the method of manufacturing the substrate, the insulating layer covering the substrate, the size of the opening diameter of the recess on the surface of the insulating layer, and the electrical resistance of the insulating layer , Indicating the electric capacity.

Table 2 shows the method for manufacturing the insulating layers of Sample Nos. 1 to 11 (method for forming the recesses) and the manufacturing conditions.

Of these samples, samples Nos. 1, 7, and 10 were used to generate a 6.6 million V impulse voltage generator (manufactured by Nichicon Corporation) (shown as test device “A” in Table 3), 400,000 V direct lightning current test. An artificial lightning current storage experiment was performed on a device (manufactured by Nichicon Corporation) (shown as test device “B” in Table 3). The results are shown in Table 3.

  From Table 3, it can be seen that each of samples Nos. 1, 7, and 10 can efficiently store the artificial lightning current. In particular, in the sample of sample number 7 that was experimented with a relatively long discharge time, the charged amount was large.

  FIG. 7 shows the relationship between the average concave portions 11a and 12a dimensions of the insulating layers 11 and 12 and the electric capacity in the series circuit. Among the experimental values, the plots of sample number 7 and sample number 4 are the samples of the example, and the other plots are samples prepared separately. From FIG. 7, it can be seen that the capacitance in the series circuit increases parabolically as the size of the opening of the recess is reduced.

(Other embodiments)
Although the embodiments of the present invention have been described as described above, it should not be understood that the descriptions and drawings constituting a part of this disclosure limit the present invention. From this disclosure, various alternative embodiments, examples and operational techniques will be apparent to those skilled in the art.

  The power storage device of the present invention can be used not only for lightning power storage but also for storing renewable energy generation such as mega solar and wind power generation, and as an effect, it eliminates instability as a large power storage system that does not require transmission lines. By doing so, the problems of the current power purchase system can be solved all at once. Furthermore, not only lightning storage, but also AD conversion is required, but as a large-scale storage battery for system power and renewable energy power, rapid power supply (charging) for EVs, including installation for each home, due to its ultra-rapid discharge (storage) capability ) As a system and EV high-capacity storage battery, a new EV use society can be created.

DESCRIPTION OF SYMBOLS ₁ ... Power storage device 2 ... Solid-state electronic storage body 2 1-2 _n ... Shunt solid-state electronic storage body (electrically distributed constant capacitor (EDCC))
DESCRIPTION OF SYMBOLS 10 ... Base | substrate 11, 12 ... Insulating layer 11a, 12a ... Recessed part 13, 14 ... Electrode

Claims (16)

A lightning rod capable of inducing lightning and atmospheric currents;
A solid-state electronic storage battery having a physical storage capacity for storing lightning and atmospheric current through the lightning rod , and
The solid-state electronic storage body is composed of a plurality of electric distributed constant capacitors that shunt lightning and atmospheric current,
Each of the electric distributed constant capacitors is
An insulating layer having a recess formed on the surface;
A pair of electrodes sandwiching the insulating layer;
With
Said recess, said evenly distributed on the surface of the insulating layer, the density of the recess, the area of 1 cm ² per surface of the insulating layer, 10 a power storage device according to claim ¹⁰ or more der Rukoto. 2. The power storage device according to claim 1, wherein the solid-state electronic power storage unit has a huge power storage capacity of 1 kF / cm ³ or more, and stores lightning and atmospheric current instantaneously for 0.5 s or less. The solid state electronic electricity storage body, the power storage device according to claim 1 or 2, characterized in that they are composed of more than 1,000 of the electrical distributed constant type capacitor. The recess, and a depth of about less opening diameter 20 nm and 0.5Nm～3nm, the insulating layer is any of claims 1 to 3, characterized in a Turkey which have a less electric resistance 100TΩ The power storage device according to claim 1 .   The power storage device according to claim 4, wherein the insulating layer covers a crystalline or amorphous layer of a metal or alloy of 100 MPa or more.   6. The power storage device according to claim 4, wherein a surface on which the concave portion is formed has an integrated nanostructure, and constitutes a parallel integrated body of nanocapacitors.   The power storage device according to claim 4, wherein the insulating layer is made of an amorphous phase having oxygen defects.   The power storage device according to any one of claims 4 to 6, wherein the insulating layer is made of an organic polymer.   The power storage device according to claim 4, wherein the insulating layer has a withstand voltage of 1 kV or more.   10. The power storage device according to claim 1, wherein the solid-state electronic power storage unit is operable at −269 ° C. to 600 ° C. 10.   The power storage device according to any one of claims 1 to 10, wherein the solid-state electronic power storage unit is configured in a square shape, a folded shape, a tape measure shape, or a spiral shape.   The power storage device according to any one of claims 1 to 11, wherein a material of at least a tip of the lightning rod is made of chromium-coated brass, aluminum, or stainless steel.   10. The device according to claim 3, further comprising a plurality of backflow prevention diodes connected between the lightning rod and each of the electric distributed constant capacitors, each having a threshold voltage of 0.4 V or less. The power storage device according to claim 1. Forming an insulating layer having recesses formed so as to be uniformly distributed on a surface , wherein the density of the recesses is 10 ¹⁰ or more per 1 cm ² of the surface area of the insulating layer ; ,
Producing an electric distributed constant capacitor by sandwiching the insulating layer between a pair of electrodes;
Producing a solid state electronic storage body having a physical storage capacity for storing lightning and atmospheric current by connecting a plurality of the electric distributed constant capacitors in parallel.   15. The step of forming the insulating layer includes forming an oxide film having a recess formed on the surface by using an anodic oxidation method in a fluorine-containing solution or in perchloric acid. A method for manufacturing a power storage device.   The method for manufacturing a power storage device according to claim 14, wherein in the step of forming the insulating layer, the insulating layer made of an organic polymer having a recess formed on the surface is formed by sputtering.